Focusing on the use of imidazolium ionic liquids and quaternary ammonium salts-based deep eutectic solvents for the separation of phenols and nitrogen-containing heteroaromatics,the role of heteroaromatics as specific...Focusing on the use of imidazolium ionic liquids and quaternary ammonium salts-based deep eutectic solvents for the separation of phenols and nitrogen-containing heteroaromatics,the role of heteroaromatics as specific sites for hydrogen bond-based separation has been investigated.These environmentally friendly solvents are known for their ability to form hydrogen bonds with heteroatoms,a key aspect in separation processes.We quantified the hydrogen bond interaction energy to reach the threshold energy for efficient O-and N-heteroaromatics separation.This article provides an in-depth study of the structural nuances of different hydrogen bonding sites and their affinity properties while conducting a comparative evaluation of the separation efficiency of ionic liquids and deep eutectic solvents from a thermodynamic perspective.Results showed that phenols with dual hydrogen bonding recognition sites were easier to separate than nitrogen-containing heteroaromatics.Imidazolium ionic liquids were more suitable for the extraction of nonbasic nitrogen-containing heteroaromatics,and quaternary ammonium salts-based deep eutectic solvents are more effective for phenols and basic nitrogen-containing heteroaromatics,which was confirmed by Fourier transform infrared spectroscopy and empirical tests.Therefore,this study provides a theoretical basis for the strategy design and selection of extractants for the efficient separation of O-and N-containing aromatic compounds.展开更多
Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADB...Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADBQ)material is designed by introducing an intramolecular hydrogen bonding(HB)strategy.The intramolecular HB(C=O⋯N-H)is formed in the reaction of 1,4-benzoquinone and 1,5-naphthalene diamine,which efficiently reduces the H-PNADBQ solubility and enhances its charge transfer in theory.In situ ultraviolet-visible analysis further reveals the insolubility of H-PNADBQ during the electrochemical cycles,enabling high durability at different current densities.Specifically,the H-PNADBQ electrode with high loading(10 mg cm^(-2))performs a long cycling life at 125 mA g^(-1)(>290 cycles).The H-PNADBQ also shows high rate capability(137.1 mAh g^(−1)at 25 A g^(−1))due to significantly improved kinetics inducted by intramolecular HB.This work provides an efficient approach toward insoluble organic electrode materials.展开更多
The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) io...The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) ions in OIHMHs is primarily confined to the low energy region,resulting in yellow or red emissions.To date,there are few reports about green emission of Sb^(3+)-doped OIHMHs.Here,we present a novel approach for regulating the luminescence of Sb^(3+) ions in 0D C_(10)H_(2)_(2)N_(6)InCl_(7)·H_(2)O via hydrogen bond network,in which water molecules act as agents for hydrogen bonding.Sb^(3+)-doped C_(10)H_(2)2N_(6)InCl_(7)·H_(2)O shows a broadband green emission peaking at 540 nm and a high photoluminescence quantum yield(PLQY)of 80%.It is found that the intense green emission stems from the radiative recombination of the self-trapped excitons(STEs).Upon removal of water molecules with heat,C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7) generates yellow emis-sion,attributed to the breaking of the hydrogen bond network and large structural distortions of excited state.Once water molecules are adsorbed by C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7),it can subsequently emit green light.This water-induced reversible emission switching is successfully used for optical security and information encryption.Our findings expand the under-standing of how the local coordination structure influences the photophysical mechanism in Sb^(3+)-doped metal halides and provide a novel method to control the STEs emission.展开更多
In this paper, the hydrogen bonding network models of konjac glucomannan (KGM) are predicted in the approach of molecular dynamics (MD). These models have been proved by experiments whose results are consistent wi...In this paper, the hydrogen bonding network models of konjac glucomannan (KGM) are predicted in the approach of molecular dynamics (MD). These models have been proved by experiments whose results are consistent with those from simulation. The results show that the hydrogen bonding network structures of KGM are stable and the key linking points of hydrogen bonding network are at the O(6) and O(2) positions on KGM ring. Moreover, acety has significant influence on hydrogen bonding network and hydrogen bonding network structures are more stable after deacetylation.展开更多
Based on the knot theory and researching of network structures of glucomannan molecules, the polysaccharides were analyzed. The link prediction analysis is to further reveal the interactions between polysaccharides, t...Based on the knot theory and researching of network structures of glucomannan molecules, the polysaccharides were analyzed. The link prediction analysis is to further reveal the interactions between polysaccharides, to elaborate QSAR of polysaccharides, and to analyze the network conformation relationships among polysaccharides. We made a classification for glucomannan molecules based on the related domestic and international theories, and investigated their network structures and application prospects. The knot theory and the link predictions not only simplify the glucomannan microscopic descriptions but also play a guiding role in predicting and regulating the structures.展开更多
Hyperbranched poly(amine-ester)s bearing self-complementary quadruple hydrogen bonding units display excellent mechanical and temperature-dependent melt rheological properties, which make them suitable as novel hot-...Hyperbranched poly(amine-ester)s bearing self-complementary quadruple hydrogen bonding units display excellent mechanical and temperature-dependent melt rheological properties, which make them suitable as novel hot-melting materials.展开更多
By means of in situ diffuse reflectance FTIR, the IR spectra of 6 coals with different ranks were obtained from room temperature to 230 ℃. A new curve fitting method was used to recognize the different hydrogen ...By means of in situ diffuse reflectance FTIR, the IR spectra of 6 coals with different ranks were obtained from room temperature to 230 ℃. A new curve fitting method was used to recognize the different hydrogen bonds in the coals, and the influence of coal ranks on the distribution of hydrogen bonds(HBs) in the coals and their thermal stability were discussed. The results show that there is another new HB(around 2514 cm -1 ) between the -SH in mercaptans or thiophenols and the nitrogen in the pyridine like compounds in the coals, and the evidence for that was provided. The controversial band of the HB between hydroxyl and the nitrogen of the pyridine like compounds was determined in the range of 3028-2984 cm -1 , and the result is consistent with but more specific than that of Painter et al .. It was found that the stability of different HBs in the coals is influenced by both coal rank and temperature. For some HBs, the higher the coal rank, the higher the stability of them. Within the temperature range of our research, the stability of the HB between the hydroxyl and the π bond increases to some extent for some coals at temperatures higher than 110 or 140 ℃.展开更多
Co-crystallization of pztcH_4 with 4,4'-bipyridine(4,4'-bipy) in pH = 3-4 and 1-2 gave two new binary molecular adducts: [(4,4'-bipy H2)(pztc H2)](1) and [(4,4'-bipy H2)(pztcH3)(Cl)]·4H2O(2),...Co-crystallization of pztcH_4 with 4,4'-bipyridine(4,4'-bipy) in pH = 3-4 and 1-2 gave two new binary molecular adducts: [(4,4'-bipy H2)(pztc H2)](1) and [(4,4'-bipy H2)(pztcH3)(Cl)]·4H2O(2), respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 5.7752(12), b = 7.9126(16), c = 9.4492(19) ?, α = 97.49(3), β = 107.71(3), γ = 94.52(3)o, V = 404.62(14) A^3, Z = 1, μ = 0.137 mm^1, Dc = 1.692 Mg/m^3, C18H12N4O8, Mr = 412.32, F(000) = 212, S = 1.025, R = 0.0360 and wR = 0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a = 17.093(3), b = 7.7665(16), c = 18.414(4) A, β = 113.36(3)o, V = 2244.1(8) A^3, Z = 4, μ = 0.244 mm^-1, Dc = 1.542 Mg/m^3, C18H21ClN4O12, Mr = 520.84, F(000) = 1080, S = 1.021, R = 0.0343 and wR = 0.0978. In compound 1, pztc H22- anions self-formed 2-D sheets by strong Oacid-H···Oacidhydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4?-bipy via N-H···Oacid interactions. In compound 2, besides the 1-D chain constructed by pztc H3-itself through strong H-bond Oacid-H···Oacid, the other chain is constructed with 4,4?-bipy H22+, Cl-anion and water molecules by moderate H-bonds and Ow-H···Cl and N-H···Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding Oacid-H···Ow to afford an interlaced 3-D network.展开更多
Based on molecular dynamics simulation results, a lauryl methacrylate polymer with drag reduction and shear resistance properties was designed, and synthesized by emulsion polymerization using 2-vinyl pyridine and met...Based on molecular dynamics simulation results, a lauryl methacrylate polymer with drag reduction and shear resistance properties was designed, and synthesized by emulsion polymerization using 2-vinyl pyridine and methyl methacrylate as the polar polymerization monomer. After ionization of lauryl methacrylate polymer, an ion-dipole interaction based drag reduction agent (DRA) was obtained. The existence of ion-dipole interaction was proven through characterization of the drag-reducing agent from its infrared (IR) spectrum. The pilot-scale reaction yield of the DRA under optimum conditions was investigated, and the drag reduction and shear resistance properties were measured. The results show that: l) The ion-dipole or hydrogen bonding interaction can form ladder-shaped chains, therefore the synthesized DRA has shear resistance properties; 2) The larger the molecular weight (MW) and more concentrated the distribution of MW, the better the drag reduction efficiency and the performance of the ionomer system was superior to that of the hydrogen bonding system; 3) With increasing shear frequency, the drag-reduction rates of both the DRAs decreased, and the drag reduction rate of the ionomer system decreased more slowly than of the corresponding hydrogen bonding system. From the point of view of drag reduction rate and shear resistance property, the ionomer system is more promising than the hydrogen bonding system展开更多
A new mono-nuclear CuII complex [Cu(DPP)(DP)Br](ClO4)H2O (DPP = 2-(3,5- dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole) has been syn- thesized with 2-(3,5-dimethyl-1H-pyrazol-1...A new mono-nuclear CuII complex [Cu(DPP)(DP)Br](ClO4)H2O (DPP = 2-(3,5- dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole) has been syn- thesized with 2-(3,5-dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline and 3,5-dimethyl-1H-pyrazole as ligands, and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic system, space group P21/c with a = 13.765(2), b = 17.044(3), c = 10.9044(16), β= 97.112(2)°, V = 2538.5(6)3, Z = 4, C22H24BrClCuN6O5, Mr = 631.37, Dc = 1.652 g/cm3, F(000) = 1276 and μ= 2.585 mm-1. In the crystal, DPP functions as a tridentate ligand and CuII ions assume a distorted square pyramidal geometry with Br atom lying on the apex, and at the same time, there is π-π stacking between adjacent complexes, which deals with two 1,10-phenanthroline plane rings. In addition to the π-π stacking, there are C-H···Br non-classic hydrogen bonds between adjacent complexes. The theoretical calculations reveal that the π-π stacking and C-H···Br non-classic hydrogen bond result in a weak anti-ferromagnetic interaction with 2J = -5.34 cm-1 and a weak ferromagnetic 2J = 5.92 cm-1, respectively. The magnetic coupling sign from the π-π stacking could be explained with McConnell I spin-polarization mechanism.展开更多
Aqueous ammonium ion batteries are regarded as eco-friendly and sustainable energy storage systems.And applicable host for NH_(4)^(+)in aqueous solution is always in the process of development.On the basis of density ...Aqueous ammonium ion batteries are regarded as eco-friendly and sustainable energy storage systems.And applicable host for NH_(4)^(+)in aqueous solution is always in the process of development.On the basis of density functional theory calcula-tions,the excellent performance of NH_(4)^(+)insertion in Prussian blue analogues(PBAs)is proposed,especially for copper hexacyanoferrate(CuHCF).In this work,we prove the outstanding cycling and rate performance of CuHCF via electrochemical analyses,delivering no capacity fading during ultra-long cycles of 3000 times and high capacity retention of 93.6%at 50 C.One of main contributions to superior performance from highly reversible redox reaction and structural change is verified during the ammoniation/de-ammoniation progresses.More importantly,we propose the NH_(4)^(+)diffusion mechanism in CuHCF based on con-tinuous formation and fracture of hydrogen bonds from a joint theoretical and experimental study,which is another essential reason for rapid charge transfer and superior NH_(4)^(+)storage.Lastly,a full cell by coupling CuHCF cathode and polyaniline anode is constructed to explore the practical application of CuHCF.In brief,the outstanding aqueous NH_(4)^(+)storage in cubic PBAs creates a blueprint for fast and sustainable energy storage.展开更多
The conversion between anamorphoses of the dihydrated glycine complex was studied by means of B3LYP/6-31++G^**. It was found that proton transfer was accompanied by hydrogen bond transfer in the process of convers...The conversion between anamorphoses of the dihydrated glycine complex was studied by means of B3LYP/6-31++G^**. It was found that proton transfer was accompanied by hydrogen bond transfer in the process of conversion between different kinds of anamorphoses. With proton transfer, the electrostatic action was notably increased and the hydrogen-bonding action was evidently strengthened when the dihydrated neutral glycine complex converts into dihydrated zwitterionic glycine complex. The activation energy required for hydrogen bond transfer between dihydrated neutral glycine complexes is very low (6.32 kJ·mol^-1); however, the hydrogen bond transfer between dihydrated zwitterionic glycine complexes is rather difficult with the required activation energy of 13.52 kJ·mol^-1 due to the relatively strong electrostatic action. The activation energy required by proton transfer is at least 27.33 kJ·mol^-1, higher than that needed for hydrogen bond transfer. The activation energy for either hydrogen bond transfer or proton transfer is in the bond-energy scope of medium-strong hydrogen bond, so the four kinds of anamorphoses of the dihydrated glycine complex could convert mutually.展开更多
A stable Sc phase is formed through hydrogen bonding between side-chain aromatic acid groups of polysiloxane: Bending of polysiloxane with N-Acetyl Latimic acid (NAA) gives a chiral S c * phase; The influence of polym...A stable Sc phase is formed through hydrogen bonding between side-chain aromatic acid groups of polysiloxane: Bending of polysiloxane with N-Acetyl Latimic acid (NAA) gives a chiral S c * phase; The influence of polymerism and hydrogen bond induction effect over mesophase is discussed. The influence of NAA over mesophase is studied.展开更多
Two zinc(Ⅱ) compounds, [Zn(L)(H2O)2]n 1 and [Zn(4,4'-bpy)(H2O)4](L) 2 (H2L = trans,trans-1,3 butadiene 1,4-dicarboxylic acid), were synthesized by hydrothermal methods and characterized by single-cryst...Two zinc(Ⅱ) compounds, [Zn(L)(H2O)2]n 1 and [Zn(4,4'-bpy)(H2O)4](L) 2 (H2L = trans,trans-1,3 butadiene 1,4-dicarboxylic acid), were synthesized by hydrothermal methods and characterized by single-crystal X-ray diffraction analyses. Compound 1 crystallizes in monoclinic, space group C2/c with a=15.4970(16), b = 5.4976(6), c = 10.7113(12) A, β=96.298(6)°, C6H8O6Zn, Mr = 241.50, V = 907.06(17) A^3, Z = 4, D, = 1.768 g/cm^3, F(000) = 488,μ = 2.703 mm^-1, S = 1.060, the final R = 0.0256 and wR = 0.0660 for 968 observed reflections with Ⅰ 〉 2σ(Ⅰ). Compound 2 crystallizes in triclinic, space group P1^- with a = 6.915(2), b = 7.166(2), c = 10.363(3) A, α = 73.250(4), β = 84.429(4), γ = 61.605(3)°, C16H2ON2O8Zn, Mr = 433.70, V = 432.1 (2) A^3, Z = 1, D, = 1.667 g/cm^3, F(000) = 224 and μ= 1.471 mm^-1, S = 1.118, the final R = 0.0486 and wR = 0.1077 for 1352 observed reflections with Ⅰ〉 2σ(Ⅰ). Upon using the assembly strategy of combination of coordination polymer chains with intermolecular hydrogen bonds, three-dimensional frameworks of complexes 1 and 2 were formed.展开更多
This paper reports that vibrational spectroscopic analysis on hYdrogen-bonding between acetone and water comprises both experimental Raman spectra and ab initio calculations on structures of various acetone/water comp...This paper reports that vibrational spectroscopic analysis on hYdrogen-bonding between acetone and water comprises both experimental Raman spectra and ab initio calculations on structures of various acetone/water complexes with changing water concentrations. The optimised geometries and wavenumbers of the neat acetone molecule and its complexes are calculated by using ab initio method at the MP2 level with 6-311+G(d,p) basis set. Changes in wavenumber position and linewidth (fullwidth at half maximum) have been explained for neat as well as binary mixtures with different mole fractions of the reference system, acetone, in terms of intermolecular hydrogen bonding. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the concentration dependent changes in the spectral features in terms of hydrogen bonding.展开更多
The practical application of silica-based composites as an alternative to commercial graphite anode materials is hampered by their large volumetric expansion,poor conductivity,and low Coulombic efficiency.In this work...The practical application of silica-based composites as an alternative to commercial graphite anode materials is hampered by their large volumetric expansion,poor conductivity,and low Coulombic efficiency.In this work,a novel silica/oxidized mesocarbon microbead/amorphous carbon(SiO2/O’MCMB/C)hierarchical structure in which SiO2 is sandwiched between spherical graphite and amorphous carbon shell was succes sfully fabricated through hydrogen bonding-assisted self-assembly and post-carbon coating method.The obtained three-layer hierarchical structure effectively accommodates the volumetric expansion of SiO2 and significantly enhances the electronic conductivity of composite materials.Moreover,the outer layer of amorphous carbon effectively increases the diffusion rate of lithium ions and promotes the formation of stable SEI film.As a result,the SiO2/O’MCMB/C composite exhibits superior electrochemical performance with a reversible capacity of 459.5 mA h/g in the first cycle,and the corresponding Coulombic efficiency is 62.8%.After 300 cycles,the capacity climbs to around 600 mA h/g.This synthetic route provides an efficient method for preparing SiO2 supported on graphite with excellent electrochemical performance,which is likely to promote its commercial applications.展开更多
To probe the behavior of hydrogen bonds in solid energetic materials, we conduct ReaxFF and SCC-DFTB molecular dynamics simulations of crystalline TATB, RDX, and DATB. By comparing the intra- and inter-molecular hydro...To probe the behavior of hydrogen bonds in solid energetic materials, we conduct ReaxFF and SCC-DFTB molecular dynamics simulations of crystalline TATB, RDX, and DATB. By comparing the intra- and inter-molecular hydrogen bond- ing rates, we find that the crystal structures are stabilized by inter-molecular hydrogen bond networks. Under high-pressure, the inter- and intra-molecular hydrogen bonds in solid TATB and DATB are nearly equivalent. The hydrogen bonds in solid TATB and DATB are much shorter than in solid RDX, which suggests strong hydrogen bond interactions existing in these energetic materials. Stretching of the C-H bond is observed in solid RDX, which may lead to further decomposition and even detonation.展开更多
The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used ...The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.展开更多
In this paper, we report on a series of computational simulations on hydrogen bonding in two ice phases (Ih and Ic) using CASTEP with PW91 and RPBE exchange-correlation based on ab initio density functional theory. ...In this paper, we report on a series of computational simulations on hydrogen bonding in two ice phases (Ih and Ic) using CASTEP with PW91 and RPBE exchange-correlation based on ab initio density functional theory. The strength of the H-bond is correlated with intramolecular O-H stretching, and the energy splitting exists for both the H-bond and covalent O-H stretching. By analyzing the dispersion relationship of to(q), we observe the separation of the longitudinal optic (LO) mode from transverse optic (TO) mode at the gamma point, seemingly interpreting the controversial two H-bond peaks in the vibrational spectrum of ice recorded by inelastic incoherent neutron scattering experiments. The test of ambient environment on phonon density of sates (PDOS) shows that the relaxed tetrahedral structure is the most stable structural configuration for water clusters.展开更多
The stable configurations and hydrogen bond nature of (H2O)n clusters (n = 3-6) have been investigated by the B3LYP method at the 6-31++g^** level. Upon calculation, four conclusions have been drawn: (1) In...The stable configurations and hydrogen bond nature of (H2O)n clusters (n = 3-6) have been investigated by the B3LYP method at the 6-31++g^** level. Upon calculation, four conclusions have been drawn: (1) In the (H2O)3-5 clusters, cyclic configurations were confirmed to be the most stable. But in the (H2O)3-4 ones, only cyclic configurations could be observed. From n = 5 ((H2O)5 clusters), three-dimensional configuration could be found: (2) In the (H2O)6 clusters, all configurations are inclined to be three-dimensional except the most stable configuration which is cyclic; (3) The stable order of (H2O)6 clusters indicates that it is the arrangement of hydrogen bond that plays a decisive role in the cluster stabilities, the zero-point energy is also important, and cluster stabilities are independent on the number of hydrogen bonds; (4) There exist strong cooperativity and superadditivity in the (H2O)n clusters.展开更多
基金support from the National Natural Science Foundation of China(22038008)the science and technology innovation project of China Shenhua Coal to Liquid and Chemical Company Limited(MZYHG-2021-01).
文摘Focusing on the use of imidazolium ionic liquids and quaternary ammonium salts-based deep eutectic solvents for the separation of phenols and nitrogen-containing heteroaromatics,the role of heteroaromatics as specific sites for hydrogen bond-based separation has been investigated.These environmentally friendly solvents are known for their ability to form hydrogen bonds with heteroatoms,a key aspect in separation processes.We quantified the hydrogen bond interaction energy to reach the threshold energy for efficient O-and N-heteroaromatics separation.This article provides an in-depth study of the structural nuances of different hydrogen bonding sites and their affinity properties while conducting a comparative evaluation of the separation efficiency of ionic liquids and deep eutectic solvents from a thermodynamic perspective.Results showed that phenols with dual hydrogen bonding recognition sites were easier to separate than nitrogen-containing heteroaromatics.Imidazolium ionic liquids were more suitable for the extraction of nonbasic nitrogen-containing heteroaromatics,and quaternary ammonium salts-based deep eutectic solvents are more effective for phenols and basic nitrogen-containing heteroaromatics,which was confirmed by Fourier transform infrared spectroscopy and empirical tests.Therefore,this study provides a theoretical basis for the strategy design and selection of extractants for the efficient separation of O-and N-containing aromatic compounds.
基金supported by the National Natural Science Foundation of China (22279063 and 52001170)the Fundamental Research Funds for the Central Universities+2 种基金Tianjin Natural Science Foundation (No. 22JCYBJC00590)the financial support by the Ministry of Education, Singapore, under its Academic Research Fund Tier 1 Thematic (RT8/22)the Haihe Laboratory of Sustainable Chemical Transformations, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin) for financial support
文摘Organic compounds have the advantages of green sustainability and high designability,but their high solubility leads to poor durability of zinc-organic batteries.Herein,a high-performance quinone-based polymer(H-PNADBQ)material is designed by introducing an intramolecular hydrogen bonding(HB)strategy.The intramolecular HB(C=O⋯N-H)is formed in the reaction of 1,4-benzoquinone and 1,5-naphthalene diamine,which efficiently reduces the H-PNADBQ solubility and enhances its charge transfer in theory.In situ ultraviolet-visible analysis further reveals the insolubility of H-PNADBQ during the electrochemical cycles,enabling high durability at different current densities.Specifically,the H-PNADBQ electrode with high loading(10 mg cm^(-2))performs a long cycling life at 125 mA g^(-1)(>290 cycles).The H-PNADBQ also shows high rate capability(137.1 mAh g^(−1)at 25 A g^(−1))due to significantly improved kinetics inducted by intramolecular HB.This work provides an efficient approach toward insoluble organic electrode materials.
基金National Natural Science Foundation of China(11974063)Graduate research innovation project,School of Optoelectronic Engineering,Chongqing University(GDYKC2023002)+1 种基金Fundamental Research Funds for the Central Universities(2022CDJQY-010)The authors extend their appreciation to the Deputyship for Research and Innovation,Ministry of Education in Saudi Arabia for funding this research work through the project no.(IFKSUOR3-073-9).
文摘The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) ions in OIHMHs is primarily confined to the low energy region,resulting in yellow or red emissions.To date,there are few reports about green emission of Sb^(3+)-doped OIHMHs.Here,we present a novel approach for regulating the luminescence of Sb^(3+) ions in 0D C_(10)H_(2)_(2)N_(6)InCl_(7)·H_(2)O via hydrogen bond network,in which water molecules act as agents for hydrogen bonding.Sb^(3+)-doped C_(10)H_(2)2N_(6)InCl_(7)·H_(2)O shows a broadband green emission peaking at 540 nm and a high photoluminescence quantum yield(PLQY)of 80%.It is found that the intense green emission stems from the radiative recombination of the self-trapped excitons(STEs).Upon removal of water molecules with heat,C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7) generates yellow emis-sion,attributed to the breaking of the hydrogen bond network and large structural distortions of excited state.Once water molecules are adsorbed by C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7),it can subsequently emit green light.This water-induced reversible emission switching is successfully used for optical security and information encryption.Our findings expand the under-standing of how the local coordination structure influences the photophysical mechanism in Sb^(3+)-doped metal halides and provide a novel method to control the STEs emission.
基金supported by the National Natural Science Foundation of China(30371009, 30471218) Science Foundation of Fujian Department of Education (JA03059)
文摘In this paper, the hydrogen bonding network models of konjac glucomannan (KGM) are predicted in the approach of molecular dynamics (MD). These models have been proved by experiments whose results are consistent with those from simulation. The results show that the hydrogen bonding network structures of KGM are stable and the key linking points of hydrogen bonding network are at the O(6) and O(2) positions on KGM ring. Moreover, acety has significant influence on hydrogen bonding network and hydrogen bonding network structures are more stable after deacetylation.
基金Supported by the National Natural Science Foundation of China(31271837 and 31071518)Specialized Research Fund for the Doctoral Program of Higher Education jointly funded by Ministry of Education(20113515110010)+2 种基金Special Research Funds from Ministry of Science and Technology(2012GA7200022)Major projects of industries,universities and research in Fujian Province(2013N5003)Natural Science Foundation of Fujian Province(2011J0101)
文摘Based on the knot theory and researching of network structures of glucomannan molecules, the polysaccharides were analyzed. The link prediction analysis is to further reveal the interactions between polysaccharides, to elaborate QSAR of polysaccharides, and to analyze the network conformation relationships among polysaccharides. We made a classification for glucomannan molecules based on the related domestic and international theories, and investigated their network structures and application prospects. The knot theory and the link predictions not only simplify the glucomannan microscopic descriptions but also play a guiding role in predicting and regulating the structures.
基金the National Natural Science Foundation of China (No.20574041)
文摘Hyperbranched poly(amine-ester)s bearing self-complementary quadruple hydrogen bonding units display excellent mechanical and temperature-dependent melt rheological properties, which make them suitable as novel hot-melting materials.
基金Supported by the National Natural Science Foundation of China(No.2 990 6 0 12)
文摘By means of in situ diffuse reflectance FTIR, the IR spectra of 6 coals with different ranks were obtained from room temperature to 230 ℃. A new curve fitting method was used to recognize the different hydrogen bonds in the coals, and the influence of coal ranks on the distribution of hydrogen bonds(HBs) in the coals and their thermal stability were discussed. The results show that there is another new HB(around 2514 cm -1 ) between the -SH in mercaptans or thiophenols and the nitrogen in the pyridine like compounds in the coals, and the evidence for that was provided. The controversial band of the HB between hydroxyl and the nitrogen of the pyridine like compounds was determined in the range of 3028-2984 cm -1 , and the result is consistent with but more specific than that of Painter et al .. It was found that the stability of different HBs in the coals is influenced by both coal rank and temperature. For some HBs, the higher the coal rank, the higher the stability of them. Within the temperature range of our research, the stability of the HB between the hydroxyl and the π bond increases to some extent for some coals at temperatures higher than 110 or 140 ℃.
基金supported by the National Natural Science Foundation of China(No.21571094)
文摘Co-crystallization of pztcH_4 with 4,4'-bipyridine(4,4'-bipy) in pH = 3-4 and 1-2 gave two new binary molecular adducts: [(4,4'-bipy H2)(pztc H2)](1) and [(4,4'-bipy H2)(pztcH3)(Cl)]·4H2O(2), respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 5.7752(12), b = 7.9126(16), c = 9.4492(19) ?, α = 97.49(3), β = 107.71(3), γ = 94.52(3)o, V = 404.62(14) A^3, Z = 1, μ = 0.137 mm^1, Dc = 1.692 Mg/m^3, C18H12N4O8, Mr = 412.32, F(000) = 212, S = 1.025, R = 0.0360 and wR = 0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a = 17.093(3), b = 7.7665(16), c = 18.414(4) A, β = 113.36(3)o, V = 2244.1(8) A^3, Z = 4, μ = 0.244 mm^-1, Dc = 1.542 Mg/m^3, C18H21ClN4O12, Mr = 520.84, F(000) = 1080, S = 1.021, R = 0.0343 and wR = 0.0978. In compound 1, pztc H22- anions self-formed 2-D sheets by strong Oacid-H···Oacidhydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4?-bipy via N-H···Oacid interactions. In compound 2, besides the 1-D chain constructed by pztc H3-itself through strong H-bond Oacid-H···Oacid, the other chain is constructed with 4,4?-bipy H22+, Cl-anion and water molecules by moderate H-bonds and Ow-H···Cl and N-H···Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding Oacid-H···Ow to afford an interlaced 3-D network.
基金supported by the Basic Research Program of China(973Program,Grant No.2008CB617508)
文摘Based on molecular dynamics simulation results, a lauryl methacrylate polymer with drag reduction and shear resistance properties was designed, and synthesized by emulsion polymerization using 2-vinyl pyridine and methyl methacrylate as the polar polymerization monomer. After ionization of lauryl methacrylate polymer, an ion-dipole interaction based drag reduction agent (DRA) was obtained. The existence of ion-dipole interaction was proven through characterization of the drag-reducing agent from its infrared (IR) spectrum. The pilot-scale reaction yield of the DRA under optimum conditions was investigated, and the drag reduction and shear resistance properties were measured. The results show that: l) The ion-dipole or hydrogen bonding interaction can form ladder-shaped chains, therefore the synthesized DRA has shear resistance properties; 2) The larger the molecular weight (MW) and more concentrated the distribution of MW, the better the drag reduction efficiency and the performance of the ionomer system was superior to that of the hydrogen bonding system; 3) With increasing shear frequency, the drag-reduction rates of both the DRAs decreased, and the drag reduction rate of the ionomer system decreased more slowly than of the corresponding hydrogen bonding system. From the point of view of drag reduction rate and shear resistance property, the ionomer system is more promising than the hydrogen bonding system
基金supported by the National Natural Science Foundation of China (No. 20971080)the Natural Science Foundation of Shandong Province (No. ZR2009BM026 and ZR2009BL002)
文摘A new mono-nuclear CuII complex [Cu(DPP)(DP)Br](ClO4)H2O (DPP = 2-(3,5- dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline, DP = 3,5-dimethyl-1H-pyrazole) has been syn- thesized with 2-(3,5-dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline and 3,5-dimethyl-1H-pyrazole as ligands, and its crystal structure was determined by X-ray crystallography. The crystal is of monoclinic system, space group P21/c with a = 13.765(2), b = 17.044(3), c = 10.9044(16), β= 97.112(2)°, V = 2538.5(6)3, Z = 4, C22H24BrClCuN6O5, Mr = 631.37, Dc = 1.652 g/cm3, F(000) = 1276 and μ= 2.585 mm-1. In the crystal, DPP functions as a tridentate ligand and CuII ions assume a distorted square pyramidal geometry with Br atom lying on the apex, and at the same time, there is π-π stacking between adjacent complexes, which deals with two 1,10-phenanthroline plane rings. In addition to the π-π stacking, there are C-H···Br non-classic hydrogen bonds between adjacent complexes. The theoretical calculations reveal that the π-π stacking and C-H···Br non-classic hydrogen bond result in a weak anti-ferromagnetic interaction with 2J = -5.34 cm-1 and a weak ferromagnetic 2J = 5.92 cm-1, respectively. The magnetic coupling sign from the π-π stacking could be explained with McConnell I spin-polarization mechanism.
基金This work is sponsored by NSAF joint Fund(U1830106)Science and Technology Innovation 2025 Major Program of Ningbo(2018B10061)National Natural Science Foundation of China(U1632114,51901205),and K.C.Wong Magna Fund in Ningbo University.
文摘Aqueous ammonium ion batteries are regarded as eco-friendly and sustainable energy storage systems.And applicable host for NH_(4)^(+)in aqueous solution is always in the process of development.On the basis of density functional theory calcula-tions,the excellent performance of NH_(4)^(+)insertion in Prussian blue analogues(PBAs)is proposed,especially for copper hexacyanoferrate(CuHCF).In this work,we prove the outstanding cycling and rate performance of CuHCF via electrochemical analyses,delivering no capacity fading during ultra-long cycles of 3000 times and high capacity retention of 93.6%at 50 C.One of main contributions to superior performance from highly reversible redox reaction and structural change is verified during the ammoniation/de-ammoniation progresses.More importantly,we propose the NH_(4)^(+)diffusion mechanism in CuHCF based on con-tinuous formation and fracture of hydrogen bonds from a joint theoretical and experimental study,which is another essential reason for rapid charge transfer and superior NH_(4)^(+)storage.Lastly,a full cell by coupling CuHCF cathode and polyaniline anode is constructed to explore the practical application of CuHCF.In brief,the outstanding aqueous NH_(4)^(+)storage in cubic PBAs creates a blueprint for fast and sustainable energy storage.
基金The project was supported by Tangshan Fundamental Research Fund (0612345A-10)
文摘The conversion between anamorphoses of the dihydrated glycine complex was studied by means of B3LYP/6-31++G^**. It was found that proton transfer was accompanied by hydrogen bond transfer in the process of conversion between different kinds of anamorphoses. With proton transfer, the electrostatic action was notably increased and the hydrogen-bonding action was evidently strengthened when the dihydrated neutral glycine complex converts into dihydrated zwitterionic glycine complex. The activation energy required for hydrogen bond transfer between dihydrated neutral glycine complexes is very low (6.32 kJ·mol^-1); however, the hydrogen bond transfer between dihydrated zwitterionic glycine complexes is rather difficult with the required activation energy of 13.52 kJ·mol^-1 due to the relatively strong electrostatic action. The activation energy required by proton transfer is at least 27.33 kJ·mol^-1, higher than that needed for hydrogen bond transfer. The activation energy for either hydrogen bond transfer or proton transfer is in the bond-energy scope of medium-strong hydrogen bond, so the four kinds of anamorphoses of the dihydrated glycine complex could convert mutually.
文摘A stable Sc phase is formed through hydrogen bonding between side-chain aromatic acid groups of polysiloxane: Bending of polysiloxane with N-Acetyl Latimic acid (NAA) gives a chiral S c * phase; The influence of polymerism and hydrogen bond induction effect over mesophase is discussed. The influence of NAA over mesophase is studied.
基金This work was supported by the National Natural Science Foundation of China (No. 20231020)
文摘Two zinc(Ⅱ) compounds, [Zn(L)(H2O)2]n 1 and [Zn(4,4'-bpy)(H2O)4](L) 2 (H2L = trans,trans-1,3 butadiene 1,4-dicarboxylic acid), were synthesized by hydrothermal methods and characterized by single-crystal X-ray diffraction analyses. Compound 1 crystallizes in monoclinic, space group C2/c with a=15.4970(16), b = 5.4976(6), c = 10.7113(12) A, β=96.298(6)°, C6H8O6Zn, Mr = 241.50, V = 907.06(17) A^3, Z = 4, D, = 1.768 g/cm^3, F(000) = 488,μ = 2.703 mm^-1, S = 1.060, the final R = 0.0256 and wR = 0.0660 for 968 observed reflections with Ⅰ 〉 2σ(Ⅰ). Compound 2 crystallizes in triclinic, space group P1^- with a = 6.915(2), b = 7.166(2), c = 10.363(3) A, α = 73.250(4), β = 84.429(4), γ = 61.605(3)°, C16H2ON2O8Zn, Mr = 433.70, V = 432.1 (2) A^3, Z = 1, D, = 1.667 g/cm^3, F(000) = 224 and μ= 1.471 mm^-1, S = 1.118, the final R = 0.0486 and wR = 0.1077 for 1352 observed reflections with Ⅰ〉 2σ(Ⅰ). Upon using the assembly strategy of combination of coordination polymer chains with intermolecular hydrogen bonds, three-dimensional frameworks of complexes 1 and 2 were formed.
基金supported by National Natural Science Foundation of China (Grant Nos.10774057 and 10974067)
文摘This paper reports that vibrational spectroscopic analysis on hYdrogen-bonding between acetone and water comprises both experimental Raman spectra and ab initio calculations on structures of various acetone/water complexes with changing water concentrations. The optimised geometries and wavenumbers of the neat acetone molecule and its complexes are calculated by using ab initio method at the MP2 level with 6-311+G(d,p) basis set. Changes in wavenumber position and linewidth (fullwidth at half maximum) have been explained for neat as well as binary mixtures with different mole fractions of the reference system, acetone, in terms of intermolecular hydrogen bonding. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the concentration dependent changes in the spectral features in terms of hydrogen bonding.
基金supported by the National Key Research and Development Program of China (No.2016YFB0100511)
文摘The practical application of silica-based composites as an alternative to commercial graphite anode materials is hampered by their large volumetric expansion,poor conductivity,and low Coulombic efficiency.In this work,a novel silica/oxidized mesocarbon microbead/amorphous carbon(SiO2/O’MCMB/C)hierarchical structure in which SiO2 is sandwiched between spherical graphite and amorphous carbon shell was succes sfully fabricated through hydrogen bonding-assisted self-assembly and post-carbon coating method.The obtained three-layer hierarchical structure effectively accommodates the volumetric expansion of SiO2 and significantly enhances the electronic conductivity of composite materials.Moreover,the outer layer of amorphous carbon effectively increases the diffusion rate of lithium ions and promotes the formation of stable SEI film.As a result,the SiO2/O’MCMB/C composite exhibits superior electrochemical performance with a reversible capacity of 459.5 mA h/g in the first cycle,and the corresponding Coulombic efficiency is 62.8%.After 300 cycles,the capacity climbs to around 600 mA h/g.This synthetic route provides an efficient method for preparing SiO2 supported on graphite with excellent electrochemical performance,which is likely to promote its commercial applications.
基金Project supported by the National Natural Science Foundation of China(Grant No.11176020)the Fund from the China Academy of Engineering Physics,China(Grant No.2011A0302014)
文摘To probe the behavior of hydrogen bonds in solid energetic materials, we conduct ReaxFF and SCC-DFTB molecular dynamics simulations of crystalline TATB, RDX, and DATB. By comparing the intra- and inter-molecular hydrogen bond- ing rates, we find that the crystal structures are stabilized by inter-molecular hydrogen bond networks. Under high-pressure, the inter- and intra-molecular hydrogen bonds in solid TATB and DATB are nearly equivalent. The hydrogen bonds in solid TATB and DATB are much shorter than in solid RDX, which suggests strong hydrogen bond interactions existing in these energetic materials. Stretching of the C-H bond is observed in solid RDX, which may lead to further decomposition and even detonation.
文摘The concept of resonance-assisted hydrogen bonds(RAHBs)highlights the synergistic interplay between theπ-resonance and hydrogen bonding interactions.This concept has been well-accepted in academia and is widely used in practice.However,it has been argued that the seemingly enhanced intramolecular hydrogen bonding(IMHB)in unsaturated compounds may simply be a result of the constraints imposed by theσ-skeleton framework.Thus,it is crucial to estimate the strength of IMHBs.In this work,we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone.One approach is the block-localized wavefunction(BLW)method,which is a variant of the ab initio valence bond(VB)theory.Using this approach,it is possible to derive the geometries and energetics with resonance shut down.The other approach is Edmiston’s truncated localized molecular orbital(TLMO)technique,which monitors the energy changes by removing the delocalization tails from localized molecular orbitals.The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced byπ-resonance,and that this enhancement is not a result ofσconstraints.
基金Project supported by the National Natural Science Foundation of China (Grant No.11075094)
文摘In this paper, we report on a series of computational simulations on hydrogen bonding in two ice phases (Ih and Ic) using CASTEP with PW91 and RPBE exchange-correlation based on ab initio density functional theory. The strength of the H-bond is correlated with intramolecular O-H stretching, and the energy splitting exists for both the H-bond and covalent O-H stretching. By analyzing the dispersion relationship of to(q), we observe the separation of the longitudinal optic (LO) mode from transverse optic (TO) mode at the gamma point, seemingly interpreting the controversial two H-bond peaks in the vibrational spectrum of ice recorded by inelastic incoherent neutron scattering experiments. The test of ambient environment on phonon density of sates (PDOS) shows that the relaxed tetrahedral structure is the most stable structural configuration for water clusters.
基金Project supported by the Natural Science Foundation of Tangshan Teacher’s College (No. 04C06)
文摘The stable configurations and hydrogen bond nature of (H2O)n clusters (n = 3-6) have been investigated by the B3LYP method at the 6-31++g^** level. Upon calculation, four conclusions have been drawn: (1) In the (H2O)3-5 clusters, cyclic configurations were confirmed to be the most stable. But in the (H2O)3-4 ones, only cyclic configurations could be observed. From n = 5 ((H2O)5 clusters), three-dimensional configuration could be found: (2) In the (H2O)6 clusters, all configurations are inclined to be three-dimensional except the most stable configuration which is cyclic; (3) The stable order of (H2O)6 clusters indicates that it is the arrangement of hydrogen bond that plays a decisive role in the cluster stabilities, the zero-point energy is also important, and cluster stabilities are independent on the number of hydrogen bonds; (4) There exist strong cooperativity and superadditivity in the (H2O)n clusters.